EP0552759A1 - Process for preparation of 4,6-dialkoxypyrimidines - Google Patents
Process for preparation of 4,6-dialkoxypyrimidines Download PDFInfo
- Publication number
- EP0552759A1 EP0552759A1 EP93100884A EP93100884A EP0552759A1 EP 0552759 A1 EP0552759 A1 EP 0552759A1 EP 93100884 A EP93100884 A EP 93100884A EP 93100884 A EP93100884 A EP 93100884A EP 0552759 A1 EP0552759 A1 EP 0552759A1
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- Prior art keywords
- general formula
- reaction
- process according
- anhydride
- preparation
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
- C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
- C07D239/52—Two oxygen atoms
Definitions
- the invention relates to a new process for the preparation of 4,6-dialkoxypyrimidines of the general formula wherein R1 and R2 represent a C1-C4 alkyl group and R3 represent a hydrogen atom or a C1-C4 alkyl group, starting from a propanediimidate and an anhydride.
- the object of the invention was to eliminate these disadvantages and to provide a simple, ecological and economically viable process for the preparation of 2-substituted and 2-unsubstituted 4,6-dialkoxypyrimidines.
- the process is carried out in such a way that a propanediimidate of the formula wherein R1 and R2 have the meaning given with an anhydride the general formula wherein R3 has the meaning given and R4 is a C1-C4 alkyl group, converted into the product according to formula I.
- Propane diimidate as a starting material for the process, can be prepared in a simple manner starting from a propane diimidate dihydrochloride in accordance with EP-PS 024 200.
- Propanediimidate dihydrochloride can e.g. can be synthesized in a simple manner according to K. Hartke & H.G. Müller, Arch. Pharm. (Weinheim), 1988, 321, pp. 863-871.
- propane diimidate dimethyl 1,3-propane diimidate, in which R 1 and R 2 represent a methyl group, for the process.
- the anhydrides are commercially available or can be prepared from the corresponding acid using standard processes.
- anhydrides for the process are, for example: formyl acetate, in which R3 is a hydrogen atom and R4 is a methyl group and acetic anhydride, in which R3 and R4 are each a methyl group.
- the propanediimidate and the anhydride are expediently used in equimolar amounts.
- reaction is expediently carried out in the presence of a base, such as ammonia or other amines, preferably in the presence of ammonia.
- a base such as ammonia or other amines
- the reaction is conveniently carried out at a temperature of 0 to 100 ° C, preferably 0 to 40 ° C.
- the reaction is expediently carried out at a pH of 5 to 8, preferably 6 to 7.
- Inert solvents are suitable as solvents for the process, such as, for example, diethyl ether, methylene chloride, acetonitrile, toluene or mixtures of these.
- Water-immiscible solvents such as, for example, methylene chloride, diethyl ether or a mixture of these, are preferably used.
- Example 2 As in Example 1, 5 g of dimethyl-1,3-propanediimidate dihydrochloride were treated and taken up in CH2Cl2. After adding 2.6 g of acetic anhydride, the solution was refluxed for two hours. After metering in NH 3 until the reaction was neutral with moistened pH paper, the mixture was refluxed for a further hour, allowed to cool and 5 ml of water added. After distilling off CH2Cl2 on a rotary evaporator, the precipitated product was filtered off, washed with a little water and dried at room temperature at 26 mbar.
Abstract
Beschrieben wird ein Verfahren zur Herstellung von 4,6-Dialkoxypyrimidinen der allgemeinen Formel <IMAGE> ausgehend von einem Propandiimidat der allgemeinen Formel <IMAGE> und einem Anhydrid der allgemeinen Formel <IMAGE>A process is described for the preparation of 4,6-dialkoxypyrimidines of the general formula <IMAGE> starting from a propanediimidate of the general formula <IMAGE> and an anhydride of the general formula <IMAGE>
Description
Die Erfindung betrifft ein neues Verfahren zur Herstellung von 4,6-Dialkoxypyrimidinen der allgemeinen Formel
worin R₁ und R₂ eine C₁-C₄-Alkylgruppe und R₃ ein Wasserstoffatom oder eine C₁-C₄-Alkylgruppe bedeuten, ausgehend von einem Propandiimidat und einem Anhydrid.The invention relates to a new process for the preparation of 4,6-dialkoxypyrimidines of the general formula
wherein R₁ and R₂ represent a C₁-C₄ alkyl group and R₃ represent a hydrogen atom or a C₁-C₄ alkyl group, starting from a propanediimidate and an anhydride.
Diese 4,6-Dialkoxypyrimidine können durch bekannte Reaktionen, z.B. durch Nitrierung mit anschliessender Reduktion, in die 5-Aminopyrimidine überführt werden, welche beispielsweise wichtige Zwischenprodukte zur Herstellung von Herbiziden darstellen (EP-PS 195 259).These 4,6-dialkoxypyrimidines can be synthesized by known reactions, e.g. by nitration with subsequent reduction, into which 5-aminopyrimidines are converted, which are, for example, important intermediates for the preparation of herbicides (EP-PS 195 259).
Bekannt ist die Herstellung von in 2-Stellung unsubstituiertem 4,6-Dimethoxypyrimidin(Shepherd et al., J. Org. Chem., 1961, 26, S. 2764 - 2769) und die Herstellung von 2-Methyl-4,6-dimethoxypyrimidin (M. Prystas, Coll. Czech. Chem. Comm., 1967, 32, S. 4241).
Bei diesen beiden Verfahren werden die entsprechenden 4,6-Dialkoxypyrimidine, ausgehend von 4,6-Dichlorpyrimidinen durch Substitution mit Methylat hergestellt.The preparation of 4,6-dimethoxypyrimidine which is unsubstituted in the 2-position is known (Shepherd et al., J. Org. Chem., 1961, 26, pp. 2764-2769) and the preparation of 2-methyl-4,6- dimethoxypyrimidine (M. Prystas, Coll. Czech. Chem. Comm., 1967, 32, p. 4241).
In these two processes, the corresponding 4,6-dialkoxypyrimidines are prepared starting from 4,6-dichloropyrimidines by substitution with methylate.
Ein grosser Nachteil dieser beiden Verfahren besteht darin, dass zunächst die 4,6-Dichlorpyrimidine ausgehend von den entsprechenden Dihydroxypyrimidinen mit chlorierten Phosphatverbindungen synthetisiert werden müssen, wobei grosse Mengen Phosphatabfälle anfallen.A major disadvantage of these two processes is that the 4,6-dichloropyrimidines must first be synthesized with chlorinated phosphate compounds starting from the corresponding dihydroxypyrimidines, with large amounts of phosphate waste being produced.
Aufgabe der Erfindung war, diese Nachteile zu beseitigen und ein einfaches, ökologisches und wirtschaftlich gangbares Verfahren zur Herstellung von 2-substituierten und von 2-unsubstituierten 4,6-Dialkoxypyrimidinen zur Verfügung zu stellen.The object of the invention was to eliminate these disadvantages and to provide a simple, ecological and economically viable process for the preparation of 2-substituted and 2-unsubstituted 4,6-dialkoxypyrimidines.
Diese Aufgabe wurde mit dem neuen Verfahren gemäss Patentanspruch 1 gelöst.This problem was solved with the new method according to claim 1.
Erfindungsgemäss wird das Verfahren derart durchgeführt, dass man ein Propandiimidat der Formel
worin R₁ und R₂ die genannte Bedeutung haben mit einem Anhydrid der allgemeinen Formel
worin R₃ die genannte Bedeutung hat und R₄ eine C₁-C₄-Alkylgruppe bedeuten, in das Produkt gemäss Formel I überführt.According to the invention, the process is carried out in such a way that a propanediimidate of the formula
wherein R₁ and R₂ have the meaning given with an anhydride the general formula
wherein R₃ has the meaning given and R₄ is a C₁-C₄ alkyl group, converted into the product according to formula I.
Propandiimidat, als Edukt für das Verfahren, kann ausgehend von einem Propandiimidat-Dihydrochlorid auf einfache Weise gemäss der EP-PS 024 200 hergestellt werden. Propandiimidat-Dihydrochlorid kann z.B. auf einfache Weise gemäss K. Hartke & H. G. Müller, Arch. Pharm. (Weinheim), 1988, 321, S. 863 - 871 synthetisiert werden.Propane diimidate, as a starting material for the process, can be prepared in a simple manner starting from a propane diimidate dihydrochloride in accordance with EP-PS 024 200. Propanediimidate dihydrochloride can e.g. can be synthesized in a simple manner according to K. Hartke & H.G. Müller, Arch. Pharm. (Weinheim), 1988, 321, pp. 863-871.
Zweckmässig wird als Propandiimidat Dimethyl-1,3-propandiimidat, worin R₁ und R₂ eine Methylgruppe bedeuten, für das Verfahren eingesetzt.Expediently used as propane diimidate is dimethyl 1,3-propane diimidate, in which R 1 and R 2 represent a methyl group, for the process.
Die Anhydride sind käuflich oder können aus der entsprechenden Säure nach Standardverfahren hergestellt werden.The anhydrides are commercially available or can be prepared from the corresponding acid using standard processes.
Wird Formylacetat als Anhydrid für das Verfahren eingesetzt, kann dieses beispielsweise gemäss Muramatsu et al., Bull. Chem. Soc. Jpn., 1965, 38, S. 244 hergestellt werden.If formyl acetate is used as the anhydride for the process, this can be done, for example, according to Muramatsu et al., Bull. Chem. Soc. Jpn., 1965, 38, p. 244.
Die zweckmassigen Anhydride für das Verfahren sind z.B.: Formylacetat, worin R₃ ein Wasserstoffatom und R₄ eine Methylgruppe bedeutet und Essigsäureanhydrid, worin R₃ und R₄ jeweils eine Methylgruppe bedeuten.The appropriate anhydrides for the process are, for example: formyl acetate, in which R₃ is a hydrogen atom and R₄ is a methyl group and acetic anhydride, in which R₃ and R₄ are each a methyl group.
Zweckmässig wird das Propandiimidat und das Anhydrid in äquimolaren Mengen eingesetzt.The propanediimidate and the anhydride are expediently used in equimolar amounts.
Zweckmässig wird die Umsetzung in Gegenwart einer Base, wie beispielsweise Ammoniak oder anderen Aminen durchgeführt, vorzugsweise in Gegenwart von Ammoniak.The reaction is expediently carried out in the presence of a base, such as ammonia or other amines, preferably in the presence of ammonia.
Die Umsetzung wird zweckmassig bei einer Temperatur von 0 bis 100°C, vorzugsweise von 0 bis 40°C, durchgeführt.The reaction is conveniently carried out at a temperature of 0 to 100 ° C, preferably 0 to 40 ° C.
Zweckmässig wird die Umsetzung bei einem pH-Wert von 5 bis 8, vorzugsweise von 6 bis 7, durchgeführt.The reaction is expediently carried out at a pH of 5 to 8, preferably 6 to 7.
Als Lösungsmittel sind für das Verfahren inerte Lösungsmittel geeignet, wie beispielsweise Diethylether, Methylenchlorid, Acetonitril, Toluol oder Gemische von diesen. Vorzugsweise werden nicht wassermischbare Lösungsmittel eingesetzt, wie beispielsweise Methylenchlorid, Diethylether oder eine Mischung von diesen.Inert solvents are suitable as solvents for the process, such as, for example, diethyl ether, methylene chloride, acetonitrile, toluene or mixtures of these. Water-immiscible solvents, such as, for example, methylene chloride, diethyl ether or a mixture of these, are preferably used.
Nach einer üblichen Umsetzung von 1 bis 4 h kann dann das Produkt gemäss Formel I mittels fachmännisch üblichen Methoden aufgearbeitet werden.After a customary reaction of 1 to 4 h, the product according to formula I can then be worked up using methods which are customary in the art.
5,0 g Dimethyl-1,3-propandiimidat-Dihydrochlorid wurde unter kräftigem Rühren zu einem Gemisch von 25 ml CH₂Cl₂ und 25 ml einer wässrigen K₂CO₃-Lösung (300 g K₂CO₃/l Lösung) gegeben. Nach 5 min wurde die organische Phase abgetrennt und die Wasserphase mit 10 ml CH₂Cl₂ extrahiert. Die vereinigten organischen Phasen wurden über Na₂SO₄ getrocknet und filtriert. Ein frisch bereitetes Gemisch von 2,5 g Formylacetat (hergestellt aus Acetylchlorid und Natriumformiat gemäss Muramatsu et al., Bull. Chem. Soc. Jpn, 1965, 38, S. 244) in 2 ml Diethylether wurde bei 0°C zur obigen Lösung des Diimidats gegeben und während zwei Stunden bei dieser Temperatur gerührt. Man leitete eine kleine Menge Ammoniakgas ein (oder fügte etherische Ammoniaklösung hinzu), so dass das Reaktionsgemisch mit angefeuchtetem pH-Papier eine etwa neutrale Reaktion zeigte. Nach einer weiteren Stunde Rühren bei 0°C wurden 10 ml Wasser hinzugefügt. Die organische Phase wurde abgetrennt, über Na₂SO₄ getrocknet und schonend eingeengt. Nach Destillation im Kugelrohrofen (Produktfraktion: 110°C/16 mbar) erhielt man das Produkt als farbloses Öl, das beim Stehenlassen allmählich erstarrte. Ausbeute: 2,4 g = 66,3% bezogen auf das eingesetzte Dihydrochlorid bei einem Produktgehalt von 96% (GC).5.0 g of dimethyl-1,3-propanediimidate dihydrochloride was added with vigorous stirring to a mixture of 25 ml of CH₂Cl₂ and 25 ml of an aqueous K₂CO₃ solution (300 g K₂CO₃ / l solution). After 5 min the organic phase was separated and the water phase extracted with 10 ml CH₂Cl₂. The combined organic phases were dried over Na₂SO₄ and filtered. A freshly prepared mixture of 2.5 g of formyl acetate (prepared from acetyl chloride and sodium formate according to Muramatsu et al., Bull. Chem. Soc. Jpn, 1965, 38, p. 244) in 2 ml of diethyl ether became the above solution at 0 ° C. of the diimidate and stirred for two hours at this temperature. A small amount of ammonia gas was bubbled in (or ethereal ammonia solution was added) so that the reaction mixture with a dampened pH paper showed an approximately neutral reaction. After stirring for another hour at 0 ° C, 10 ml of water was added. The organic phase was separated, dried over Na₂SO₄ and gently concentrated. After distillation in a Kugelrohr oven (product fraction: 110 ° C / 16 mbar), the product was obtained as a colorless oil which gradually solidified on standing. Yield: 2.4 g = 66.3% based on the dihydrochloride used with a product content of 96% (GC).
Wie bei Beispiel 1 wurden 5 g Dimethyl-1,3-propandiimidat-Dihydrochlorid behandelt und in CH₂Cl₂ aufgenommen. Nach Zugabe von 2,6 g Essigsäureanhydrid wurde die Lösung während zwei Stunden rückflussiert. Nach Zudosieren von NH₃ bis zur neutralen Reaktion mit angefeuchtetem pH-Papier rückflussierte man eine weitere Stunde, liess abkühlen und fügte 5 ml Wasser hinzu. Nach Abdestillieren von CH₂Cl₂ am Rotationsverdampfer wurde das ausgefallende Produkt abfiltriert, mit wenig Wasser gewaschen und bei Raumtemperatur bei 26 mbar getrocknet. Man erhielt 2,2 g weisses kristallines Produkt (Smp: 51 - 52°C) mit einem Gehalt von 98% (GC) was einer Ausbeute von 56,3% bezogen auf das Dihydrochlorid entsprach.
Durch Extraktion der Wasserphase und anschliessende Säulenchromatographie liess sich die Ausbeute auf 68% erhöhen.As in Example 1, 5 g of dimethyl-1,3-propanediimidate dihydrochloride were treated and taken up in CH₂Cl₂. After adding 2.6 g of acetic anhydride, the solution was refluxed for two hours. After metering in NH 3 until the reaction was neutral with moistened pH paper, the mixture was refluxed for a further hour, allowed to cool and 5 ml of water added. After distilling off CH₂Cl₂ on a rotary evaporator, the precipitated product was filtered off, washed with a little water and dried at room temperature at 26 mbar. 2.2 g of white crystalline product (mp: 51-52 ° C.) with a content of 98% (GC) were obtained, which corresponded to a yield of 56.3% based on the dihydrochloride.
The yield could be increased to 68% by extraction of the water phase and subsequent column chromatography.
Claims (6)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH18892 | 1992-01-23 | ||
| CH188/92 | 1992-01-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0552759A1 true EP0552759A1 (en) | 1993-07-28 |
Family
ID=4181269
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP93100884A Withdrawn EP0552759A1 (en) | 1992-01-23 | 1993-01-21 | Process for preparation of 4,6-dialkoxypyrimidines |
Country Status (15)
| Country | Link |
|---|---|
| US (1) | US5276152A (en) |
| EP (1) | EP0552759A1 (en) |
| JP (1) | JPH05279345A (en) |
| KR (1) | KR930016405A (en) |
| CN (1) | CN1075715A (en) |
| AU (1) | AU656252B2 (en) |
| CA (1) | CA2087741A1 (en) |
| CZ (1) | CZ393392A3 (en) |
| FI (1) | FI930237A (en) |
| HU (1) | HUT63396A (en) |
| IL (1) | IL104477A0 (en) |
| NO (1) | NO930223L (en) |
| PL (1) | PL297518A1 (en) |
| SK (1) | SK393392A3 (en) |
| ZA (1) | ZA9210103B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5821368A (en) * | 1996-07-18 | 1998-10-13 | Lonza Ag | Method for preparing pyrimidin-2-ylacetic acid esters |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4903183A (en) * | 1987-10-21 | 1990-02-20 | Hitachi, Ltd. | Power supply for a magnetron |
| WO2003033474A1 (en) * | 2001-10-17 | 2003-04-24 | Lonza Ltd. | Process for the preparation of (pyrimmidin-2-yl)methyl ketones |
| US10113577B2 (en) * | 2013-11-22 | 2018-10-30 | Illinois Tool Works Inc. | Locking pin and grommet fastener assembly |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0279366A2 (en) * | 1987-02-18 | 1988-08-24 | Hoechst Aktiengesellschaft | Process for the preparation of pyrimidines |
| DE3939965A1 (en) * | 1989-12-02 | 1991-06-06 | Bayer Ag | Prodn. of 6-alkoxy-2-alkyl-4-hydroxy-pyrimidine derivs. - useful as insecticide intermediates, comprises cyclising new alkano:imido-substd. carbamoyl-acetate |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AR225772A1 (en) * | 1979-08-14 | 1982-04-30 | Du Pont | NEW 3-AMINO-3-ALCOXI-N-CIANO-2-ALKYL PROPENIMIDATE AND PROCEDURES FOR ITS PREPARATION AND OF PYRIMIDINES STARTING FROM THOSE |
| ZA917307B (en) * | 1990-09-15 | 1992-05-27 | Hoechst Ag | Process for the preparation of aminopyrimidines |
-
1992
- 1992-12-28 SK SK3933-92A patent/SK393392A3/en unknown
- 1992-12-28 CZ CS923933A patent/CZ393392A3/en unknown
- 1992-12-30 AU AU30479/92A patent/AU656252B2/en not_active Ceased
- 1992-12-30 ZA ZA9210103A patent/ZA9210103B/en unknown
-
1993
- 1993-01-19 JP JP5006595A patent/JPH05279345A/en not_active Withdrawn
- 1993-01-21 KR KR1019930000800A patent/KR930016405A/en not_active Application Discontinuation
- 1993-01-21 EP EP93100884A patent/EP0552759A1/en not_active Withdrawn
- 1993-01-21 CA CA002087741A patent/CA2087741A1/en not_active Abandoned
- 1993-01-21 CN CN93101266A patent/CN1075715A/en active Pending
- 1993-01-21 FI FI930237A patent/FI930237A/en not_active Application Discontinuation
- 1993-01-21 IL IL104477A patent/IL104477A0/en unknown
- 1993-01-21 US US08/006,524 patent/US5276152A/en not_active Expired - Fee Related
- 1993-01-22 NO NO93930223A patent/NO930223L/en unknown
- 1993-01-22 HU HU9300183A patent/HUT63396A/en unknown
- 1993-01-22 PL PL29751893A patent/PL297518A1/en unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0279366A2 (en) * | 1987-02-18 | 1988-08-24 | Hoechst Aktiengesellschaft | Process for the preparation of pyrimidines |
| DE3939965A1 (en) * | 1989-12-02 | 1991-06-06 | Bayer Ag | Prodn. of 6-alkoxy-2-alkyl-4-hydroxy-pyrimidine derivs. - useful as insecticide intermediates, comprises cyclising new alkano:imido-substd. carbamoyl-acetate |
Non-Patent Citations (3)
| Title |
|---|
| COLLECTION OF CZECHOSLOVAK CHEMICAL COMMUNICATIONS Bd. 32, 1967, Seiten 4241 - 4259 M. PRYSTAS 'Nucleic acid components and their analogues. CII.' * |
| PATENT ABSTRACTS OF JAPAN vol. 10, no. 328 (C-383)(2384) 7. November 1986 & JP-A-61 134 378 ( NISSAN CHEM. IND. LTD ) 21. Juni 1986 * |
| THE JOURNAL OF ORGANIC CHEMISTRY Bd. 26, Nr. 8, August 1961, COLUMBUS OHIO Seiten 2764 - 2769 R.G. SHEPHERD ET AL. 'Sulfanilamidopyrimidines. I' * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5821368A (en) * | 1996-07-18 | 1998-10-13 | Lonza Ag | Method for preparing pyrimidin-2-ylacetic acid esters |
Also Published As
| Publication number | Publication date |
|---|---|
| FI930237A0 (en) | 1993-01-21 |
| KR930016405A (en) | 1993-08-26 |
| HU9300183D0 (en) | 1993-04-28 |
| NO930223D0 (en) | 1993-01-22 |
| FI930237A (en) | 1993-07-24 |
| IL104477A0 (en) | 1993-05-13 |
| AU656252B2 (en) | 1995-01-27 |
| JPH05279345A (en) | 1993-10-26 |
| HUT63396A (en) | 1993-08-30 |
| CN1075715A (en) | 1993-09-01 |
| PL297518A1 (en) | 1993-08-23 |
| CZ393392A3 (en) | 1993-10-13 |
| ZA9210103B (en) | 1993-08-03 |
| CA2087741A1 (en) | 1993-07-24 |
| NO930223L (en) | 1993-07-26 |
| US5276152A (en) | 1994-01-04 |
| SK393392A3 (en) | 1995-09-13 |
| AU3047992A (en) | 1993-07-29 |
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